Differential selectivity in electrochemical oxidation of ascorbic acid and hydrogen peroxide at the surface of functionalized ormosil-modified electrodes

Abstract

Functionalized ormosil-modified electrodes have been developed for electroanalytical applications. The functionalized ormosil-modified electrodes are made by encapsulating potassium ferricyanide/potassium ferrocyanide within ormosil film derived from an optimum composition of 3-aminopropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane and phenyltrimethoxy silane in acidic medium in absence of Nafion/crown ether (system 1), in the presence of Nafion (system 2) and in the presence of dibenzo-18-crown-6 (system 3). Another modified electrode (system 4) is also developed using the reaction product of potassium ferricyanide, 3-aminopropyltrimethoxysilane and either tetrahydrofuran (THF) or cyclohexanone followed by ormosil formation in the presence of 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane and phenyltrimethoxy silane in acidic medium. The electrochemical oxidation of hydrogen peroxide and ascorbic acid conducted at the surface of these four types of functionalized electrodes shows very interesting observations on the selective sensing of ascorbic acid and peroxide. The results based on cyclic voltammetry justify the relative performances on the kinetics of hydrogen peroxide oxidation and reduction. System 3 shows relatively much better oxidation kinetics of hydrogen peroxide as compared to other three systems with relatively weak reduction kinetics whereas system 4 shows relatively faster reduction kinetics of hydrogen peroxide as compared to other three systems. Similarly system 4 shows excellent response to ascorbic acid whereas system 3 shows insensitivity to ascorbic acid under similar experimental conditions. Typical response curve for the analysis of hydrogen peroxide and ascorbic acid using system 3 and system 4 respectively are reported. The results show that system 3 is the best for probing hydrogen peroxide with lowest detection limit of 0.5 μM without any interference from ascorbic acid as commonly encountered using many conventional and chemically modified electrodes.